KR100746054B1 - Rubber composition for footwear - Google Patents

Abstract

The present invention provides a rubber composition for shoes, comprising: (1) 100 parts by weight of a rubbery polymer; And (2) 100 parts by weight of one or more modified polymers selected from conjugated diene-based polymers, copolymers of conjugated diene-based monomers and vinyl aromatic hydrocarbons, or modified polymers of hydrogenation products thereof, each having one or more functional group-containing atom groups bonded thereto; And 1 to 150 parts by weight of a master batch obtained by kneading 5 to 300 parts by weight of an inorganic filler. The rubber composition for shoes of the present invention is excellent in tear strength and abrasion resistance, and also excellent in adhesion to nylon, leather, and EVA, which are shoes materials. Due to these features, the compositions of the present invention are very effective materials for various shoe sole materials.

Description

Rubber composition for shoes {RUBBER COMPOSITION FOR FOOTWEAR}

The present invention relates to a rubbery polymer composition comprising a master batch component and a rubbery polymer component obtained by premixing a modified polymer having a functional group-containing atom group and an inorganic filler, in particular a novel rubber for rubber having excellent tear strength, wear resistance and adhesion. To a composition.

Usually, rubber polymers are used as raw materials for footwear in various footwear applications. In order to impart the required characteristics according to the use, a rubber composition mainly composed of a rubbery polymer and in which various inorganic fillers, additives, colorants and the like are blended is used as a raw material. In various rubber products such as shoes, white fillers such as silica are widely used as reinforcing agents to improve the appearance of the product. However, when silica is used as a reinforcing filler, the affinity for rubber is lower than that of ordinary carbon black. Therefore, the dispersibility of silica in rubber is not necessarily good, and such poor dispersibility is likely to deteriorate abrasion resistance and reduce mechanical strength. Then, in order to obtain a high reinforcement like the reinforcement of carbon black, a silane coupling agent represented by bis- (3-triethoxysilylpropyl) tetrasulfide in order to improve the dispersion of silica in incorporating silica into the rubber composition. This increases the cost.

Features required as shoe sole materials include good wear resistance and wet slip resistance, and good adhesion of the midsole to the top.

In addition, the use of silica powder causes the powder to be blown during oral manufacturing, resulting in poor workability. Also, in recent years, in view of improving the working environment of shoe manufacturing plants, there has been an increasing trend of changing the adhesive used for shoe manufacturing from an organic solvent to an aqueous adhesive. However, the present situation is that a satisfactory adhesive strength has not yet been obtained.

As a method for improving the rubber composition, Patent Document 1 discloses that a shoe sole having excellent colorability and wear resistance is obtained by restricting silica and a silane coupling agent and mixing a thermoplastic resin with rubber. However, even in the case of using an aqueous adhesive, a rubber composition having excellent adhesive strength has not yet been obtained. Patent document 2 discloses a lightweight wear resistant shoe sole material comprising high cis polybutadiene, styrene resin and silica. Patent document 3 discloses a rubber composition for shoes having improved wear resistance by using a specific polysiloxane compound. In addition, Patent Document 4 discloses a rubber composition for shoes having excellent abrasion resistance and wet sliding resistance by blending a modified polymer having a specific structure and silica. In all cases, however, a rubber composition having excellent adhesive strength was not always obtained even when using an aqueous adhesive.

Patent documents 5 and 6 disclose rubber compositions using a master batch comprising a modified polymer and a reinforcing filler. However, the adhesive strength which is an important feature as a rubber composition for shoes is not explained at all.

Patent Document 1: JP-A-62-137002

Patent Document 2: JP-A-2000-236905

Patent Document 3: JP-A-2002-191401

Patent Document 4: JP-A-2002-284931

Patent Document 5: JP-A-8-231766

Patent Document 6: JP-A-2000-136269

The present invention comprises a rubbery polymer and an inorganic filler by preparing a master batch of inorganic filler and a modified polymer having a functional group-containing atomic group bonded thereto, and producing a rubber composition comprising the master batch and the rubbery polymer, wherein the tear strength, It provides a rubber composition for shoes that is excellent in wear resistance and adhesion and can improve the working environment of a shoe manufacturing plant.

We have conducted in-depth studies in improving the properties of the conjugated diene-based polymers, copolymers comprising vinyl aromatic hydrocarbons and conjugated diene-based monomers, or hydrogenated products thereof, and the rubber compositions of the inorganic fillers. As a result, in the production of a rubber composition comprising a rubbery polymer and a filler, by using a master batch in which a modified polymer having a specific functional group is pre-kneaded with an inorganic filler, a rubber composition for shoes having excellent tear strength, wear resistance and adhesion can be obtained. It was found that this was obtained, thus completing the present invention.

That is, the present invention is as follows:

1. A rubber composition for shoes, comprising:

Component (1): 100 parts by weight of a rubbery polymer; And

Component (2): 100 weights of one or more modified polymers selected from conjugated diene-based polymers, copolymers of conjugated diene-based monomers and vinyl aromatic hydrocarbons, or modified polymers of hydrogenated products thereof, each having one or more functional group-containing atom groups bound thereto 1 to 150 parts by weight of a master batch obtained by kneading 5 parts and 5 to 300 parts by weight of an inorganic filler;

2. The rubber composition for footwear according to the above 1, wherein component (2) is obtained by feeding 5 to 300 parts by weight of an inorganic filler into a kneader in advance, followed by kneading, followed by addition of a modified polymer, followed by kneading. A rubber composition for footwear, in one master batch;

3. The shoe rubber composition according to the above 1, wherein the component (2) is a master batch obtained by kneading sequentially after supplying 5 to 300 parts by weight of an inorganic filler into a kneader two times or more, and then kneading them sequentially. Rubber composition for use;

4. The rubber composition for footwear according to the above 1, wherein the component (2) is supplied with 20 to 80% by weight of an inorganic filler in advance into the kneader, and then kneaded, and then a modified polymer is added, and the remaining amount is further Rubber composition for footwear, which is a master batch obtained by kneading after adding the inorganic filler;

5. The rubber composition for footwear according to 1 above, further comprising 0.1 to 150 parts by weight of an inorganic filler as component (3);

6. The rubber composition for footwear according to item 1, wherein the functional group-containing atomic group of the modified polymer is an atomic group having at least one functional group selected from the group consisting of hydroxyl group, epoxy group, amino group, imino group, silanol group and alkoxysilane group. Rubber compositions for footwear;

7. The rubber composition for footwear according to 1, wherein the modified polymer is bonded to at least one atomic group selected from the following formulas (1) to (14):

[In the above-mentioned formulas (1) to (14), N represents a nitrogen atom; Si represents a silicon atom; O represents an oxygen atom; C represents a carbon atom; H represents a hydrogen atom; R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and the hydrocarbon groups are each independently, as desired, a hydroxyl group, an epoxy group, an amino group, an imino group (a hydrocarbon having 1 to 24 carbon atoms). Group), a silanol group and an alkoxysilane group having 1 to 24 carbon atoms; Each R ³ independently represents a divalent hydrocarbon group having 1 to 48 carbon atoms, and as desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group (having a hydrocarbon group having 1 to 24 carbon atoms), a silane May have one or more functional groups selected from the group consisting of an oligo group and an alkoxysilane group having 1 to 24 carbon atoms; Each R ⁴ independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms;

8. In the rubber composition for footwear described in 1 above, when the component (2) is kneaded with the modified polymer and the inorganic filler, the compound (4) having reactivity with the functional group bonded to the modified polymer is 100 weight of the modified polymer. Rubber composition for footwear, which is a master batch obtained by further addition in an amount of 0.01 to 20 parts by weight based on parts;

9. The rubber composition for footwear according to the above 1, wherein the component (2) comprises a compound (4) having a reactivity to the kneaded product of the modified polymer and the inorganic filler with a functional group bonded to the modified polymer, the modified polymer 100 A rubber composition for shoes, which is a master batch obtained by further adding in an amount of 0.01 to 20 parts by weight based on parts by weight;

10. The rubber composition for footwear described in 1 above, wherein the modified polymer used for component (2) has a compound (4) having a reactivity with a functional group bonded to the modified polymer per equivalent of functional group bonded to the modified polymer. A rubber composition for footwear, which is a modified polymer obtained by reacting in an amount of 0.3 to 10 moles;

11. The footwear rubber composition according to the above 8 or 9, wherein the component (4) is a compound having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. Rubber compositions;

12. A process for preparing a rubber composition for shoes, comprising kneading:

Component (1): 100 parts by weight of a rubbery polymer; And

Component (2): 100 weights of one or more modified polymers selected from conjugated diene-based polymers, copolymers of conjugated diene-based monomers and vinyl aromatic hydrocarbons, or modified polymers of hydrogenated products thereof, each having one or more functional group-containing atom groups bound thereto 1 to 150 parts by weight of a master batch obtained by kneading 5 parts and 5 to 300 parts by weight of an inorganic filler;

13. The method for producing a rubber composition for shoes described in 12 above, wherein component (2) is fed with 5 to 300 parts by weight of an inorganic filler into the kneader, followed by kneading, followed by addition of a modified polymer, A method for producing a rubber composition for shoes, which is a master batch obtained by kneading;

14. The master batch obtained in the method for producing a rubber composition for footwear described in 12 above, wherein component (2) is fed into a kneader by dividing 5 to 300 parts by weight of an inorganic filler into a kneader two or more times, and then kneading sequentially. Phosphorus, a method for producing a rubber composition for shoes;

15. The master batch production method according to item 1, wherein the master batch comprises supplying 5 to 300 parts by weight of an inorganic filler into the kneader, followed by kneading, followed by addition of a modified polymer and then kneading. A method of making a batch; And

16. The process for producing a master batch according to 1 above, wherein 20 to 80% of an inorganic filler is fed into the kneader in advance, and then kneaded, followed by addition of a modified polymer, followed by kneading and further remaining amount The method of manufacturing a master batch, which comprises kneading after adding the inorganic filler.

Prepared using a master batch of inorganic polymers and modified polymers with specific functional group-containing atomic groups, the inventive rubber compositions have excellent tear strength, abrasion resistance and adhesion, even when using an aqueous adhesive, It is a rubber composition which can improve the working environment of a manufacturing plant.

To carry out the invention Best  shape

The present invention is described in detail below.

The kind of the rubbery polymer which is the component (1) constituting the rubber composition for footwear of the present invention is not particularly limited, but examples thereof include randomized conjugated diene-based polymers or hydrogenated products thereof, conjugated diene-based monomers and vinyl aromatic hydrocarbons. Copolymers or hydrogenated products thereof, block copolymers comprising conjugated diene-based monomers and vinyl aromatic hydrocarbons or hydrogenated products thereof, non-diene-based polymers, natural rubbers and the like. Specific examples thereof include butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof and styrene-isoprene block copolymer or hydrogenated product thereof. Styrenic elastomers, acrylonitrile-butadiene rubber or hydrogenated products thereof and the like. Non-diene-based polymers also include olefin elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber and ethylene-octene rubber, butyl rubber, Brominated butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber and the like. These rubbery polymers can be modified rubbers imparted with functional groups. The above-mentioned rubbery polymers may be used alone or as a mixture of two or more rubbery polymers.

Component (2) constituting the rubber composition for footwear of the present invention comprises a conjugated diene-based polymer, a copolymer comprising a conjugated diene-based monomer and a vinyl aromatic hydrocarbon, to which at least one functional group-containing atomic group is bonded, and a hydrogenated product thereof One or more modified polymers and inorganic fillers selected from the modified polymers of are rubber compositions obtained in advance as a master batch.

The modified copolymer comprising a modified conjugated diene-based polymer or conjugated diene-based monomer and a vinyl aromatic hydrocarbon for use in component (2) of the present invention comprises at least one conjugated diene-based monomer and at least one vinyl aromatic hydrocarbon It can manufacture by solution polymerization in presence. As the production method of the modified polymer of the present invention, any production method can be used as long as the polymer having the structure of the present invention can be obtained.

The conjugated diene monomer in the present invention is a diolefin having a pair of double bonds, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1, 3-butadiene, 1,3-pentadiene and 1,3-hexadiene. In particular, the general includes 1,3-butadiene and isoprene. These can be used not only individually for manufacture of a polymer but also using 2 or more types together.

Vinyl aromatic hydrocarbons also include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. These may be used alone in the preparation of the polymer as well as as a mixture of two or more kinds.

As the solvent used in the preparation of the modified polymer, hydrocarbon solvents such as aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane and isooctane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane; And aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more kinds.

In addition, the organolithium compound used in the preparation of the modified polymer is a compound in which one or more lithium atoms are bound in a molecule, such as ethyl lithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert Butyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium and the like. In addition, U.S. Patent 5,708,092, GB Patent 2,241,239, U.S. Pat. Organic alkali metal compounds such as amidolithium described in Patent 5,527,753 and the like can also be used. These may be used alone or as a mixture of two or more kinds. In addition, the organolithium compound may be added in one or more times during the polymerization in the preparation of the polymer.

In the present invention, a polar compound or a randomizing agent can be used for adjusting the polymerization rate in preparing the polymer, changing the microstructure of the conjugated diene portion in the polymer, adjusting the reactivity ratio of the conjugated diene monomer and the vinyl aromatic hydrocarbon, and the like. have. Polar compounds and randomizing agents include ethers, amines, thioethers, phosphoramides, potassium or sodium salts of alkylbenzenesulfonic acids, alkoxides of potassium or sodium, and the like.

Examples of ethers include dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and the like. Amines include tertiary amines, trimethylamines, triethylamines, tetramethylethylenediamines, other cyclic tertiary amines, and the like. Phosphines and phosphoramides include triphenylphosphine, hexamethylphosphoramide, and the like.

The polymerization temperature at the time of polymer manufacture is preferably -10 to 150 캜, more preferably 30 to 120 캜. The time required for the polymerization depends on the conditions, but is preferably 48 hours or less, particularly preferably 0.5 to 10 hours. The atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a range sufficient to keep the monomer and the solvent in the liquid phase in the polymerization temperature range described above. However, it is usually 0.2 to 2 MPa, preferably 0.3 to 1.5 MPa. The reaction temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 20 to 120 ° C, even more preferably in the range of 50 to 100 ° C. It is also desirable that impurities such as water, oxygen and carbon dioxide, which deactivate the catalyst and living polymer, are not mixed in the polymerization system.

Modified polymers of conjugated diene-based polymers or hydrogenated products thereof used in component (2) of the present invention are modified polymers of conjugated diene-based polymers having a homopolymer of a conjugated diene-based monomer or a vinyl aromatic hydrocarbon content of less than 5% by weight. The structure of the conjugated diene-based polymer or its hydrogenation product may be straight or branched. It may also be any mixture thereof. In addition, the copolymer comprising the conjugated diene-based monomer and the vinyl aromatic hydrocarbon or a hydrogenation product thereof may be a random copolymer or a block copolymer. In addition, the structure of the modified copolymer or hydrogenation product thereof may be straight chain, branched or a mixture thereof.

The vinyl aromatic hydrocarbon content of the random copolymer comprising the conjugated diene monomer and the vinyl aromatic hydrocarbon or hydrogenated product thereof used in component (2) of the present invention is usually 5 to 95% by weight, preferably 10 to 90% by weight, More preferably from 15 to 85% by weight. In addition, two or more random copolymer blocks having different vinyl aromatic hydrocarbon contents may be present in the polymer chain of the random copolymer or its hydrogenation product. In addition, one or more conjugated diene polymer blocks or hydrogenation products thereof may be present therein.

The modified polymer of the conjugated diene-based polymer or the modified copolymer of the random copolymer is obtained by adding a modifying agent to the living end of the conjugated diene-based polymer or the random copolymer.

The vinyl aromatic hydrocarbon content of the block copolymer comprising the conjugated diene monomer and the vinyl aromatic hydrocarbon or hydrogenated product thereof used in component (2) of the present invention is usually 5 to 95% by weight, preferably 10 to 90% by weight, More preferably, it is 15 to 85 weight%. If the vinyl aromatic hydrocarbon content of the block copolymer or its hydrogenated product is at least 60% by weight, preferably at least 65% by weight, it has resinous properties, and if it is less than 60% by weight, preferably less than 55% by weight, it is elastic. Has

Methods for producing block copolymers include JP-B-36-19286, JP-B-43-17979, JP-B-46-32415, JP-B-49-36957, JP-B-48-2423, JP-B -48-4106, JP-B-56-28925, JP-B-51-49567, JP-A-59-166518, JP-A-60-186577 and the like.

The modified polymer of the block copolymer used in the present invention is obtained by adding the following modifying agent to the living end of the block copolymer, and has a structure represented by the following formula:

(AB) _n -X, A- (BA) _n -X,

B- (AB) _n -X, X- (AB) _n ,

X- (AB) _n -X, XA- (BA) _n -X,

XB- (AB) _n -X, [(BA) _n ] _m -X,

[(AB) _n ] _m -X, [(BA) _n -B] _m -X and

[(AB) _n -A] _m -X

(Wherein A is a polymer block mainly containing vinyl aromatic hydrocarbons; B is a polymer block mainly containing conjugated diene-based monomers; the boundary between block A and block B does not necessarily need to be clearly distinguished; n is 1) An integer greater than or equal to 1, preferably an integer from 1 to 5, m is an integer greater than or equal to 2, preferably an integer from 2 to 11, X represents a moiety of a modifier bound to a functional group-containing atom group described below; When added by a metal chloride reaction, it is bonded to the side chain of block A and / or block B).

In the structure represented by the above-mentioned formula, the polymer block A mainly containing the vinyl aromatic hydrocarbon is preferably a vinyl aromatic hydrocarbon containing the vinyl aromatic hydrocarbon in an amount of 50% by weight or more, more preferably 70% by weight or more. Copolymer blocks of conjugated diene monomers or homopolymer blocks of vinyl aromatic hydrocarbons. Vinyl aromatic hydrocarbons may be dispersed homogeneously or in a decreasing shape. The polymer block B mainly comprising the conjugated diene monomer is a copolymer block of the conjugated diene monomer and the vinyl aromatic hydrocarbon containing the conjugated diene monomer in an amount of preferably more than 50% by weight, more preferably 60% by weight or more. Or homopolymer blocks of conjugated diene monomers.

In addition, in the modified block copolymer, a plurality of portions dispersed in a shape in which the vinyl aromatic hydrocarbon is uniformly and / or gradually reduced may coexist. The modified block copolymer used in the present invention may be any mixture of modified block copolymers represented by the above-mentioned formula.

The ratio of the vinyl aromatic hydrocarbon polymer block incorporated into the modified block copolymer (called the block ratio of the vinyl aromatic hydrocarbon) is less than 50% by weight, preferably 5 to 45% by weight, more preferably 10 To 40% by weight, and in view of maintaining the rigidity of the molded article, it is recommended that it is at least 50% by weight, preferably 50 to 97% by weight, more preferably 60 to 95% by weight, particularly preferably 70 to 92% by weight. do.

The block ratio of vinyl aromatic hydrocarbons incorporated into the block copolymer is determined by oxidatively decomposing the block copolymer using tertiary butyl hydroperoxide using osmium tetraoxide as a catalyst [I. M. KOLTHOFF, et al., J. Polym. Sci., 1, 429 (1946)] measured from the following formula using the vinyl aromatic hydrocarbon polymer block component (except for the vinyl aromatic hydrocarbon polymer block component having an average degree of polymerization of about 10 or less). can do:

Block ratio (% by weight) of vinyl aromatic hydrocarbon = (weight of vinyl aromatic hydrocarbon polymer block in block copolymer / weight of total vinyl aromatic hydrocarbon in block copolymer) x 100.

In the present invention, the fine structure (ratio of cis, trans and vinyl) of the conjugated diene portion in the modified conjugated diene polymer or the copolymer containing the conjugated diene monomer and the vinyl aromatic hydrocarbon may be optionally You can change it. The amount of vinyl bonds is not specifically limited. However, when 1,3-butadiene is used as the conjugated diene monomer, the vinyl bond amount is preferably 5 to 90%, more preferably 10 to 80%. When isoprene is used as the conjugated diene monomer or when 1,3-butadiene and isoprene are used in combination, the amount of vinyl bonds that is the sum of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 3 to 80. %, More preferably 5 to 70%. As used herein, the amount of vinyl bonds incorporated into 1,2- and 3,4-bond forms for conjugated diene-based monomers incorporated in 1,2-, 3,4- and 1,4-bond forms. It means the ratio of the conjugated diene monomer. The vinyl bonds in the modified polymer may be distributed uniformly or gradually decreasing in the polymer chain, or there may be two or more polymer blocks having different vinyl bond forms. The amount of vinyl bonds can be arbitrarily changed using the polar compound mentioned later.

However, in the case of using the hydrogenated product of the modified block copolymer, its microstructure is preferably 10 to 80%, more preferably in the case of using 1,3-butadiene as the conjugated diene monomer. 25-75% and when using isoprene as a conjugated diene type monomer or when using 1, 3- butadiene and isoprene together, the amount of a vinyl bond which is a sum total of a 1, 2- vinyl bond and a 3, 4- vinyl bond is preferable. Preferably 5 to 70%. The amount of vinyl bonds based on the conjugated diene monomers in the modified polymer can be known using a nuclear magnetic resonance apparatus (NMR).

In the production of a conjugated diene polymer or a copolymer containing a conjugated diene monomer and a vinyl aromatic hydrocarbon, when isoprene and 1,3-butadiene are used together as a conjugated diene polymer, the weight ratio of isoprene and 1,3-butadiene is Preferably it is 95/5-5/95, More preferably, it is 90/10-10/90, More preferably, it is 85/15-15/85. In particular, when obtaining a rubber composition having excellent low temperature properties, the weight ratio of isoprene and 1,3-butadiene is preferably 49/51 to 5/95, more preferably 45/55 to 10/90, even more preferably Is recommended to be 40/60 to 15/85. In the case where isoprene and 1,3-butadiene are used in combination, a rubber composition having good mechanical properties is obtained even during molding at high temperature.

Next, the modified polymer used for the component (2) used by this invention is demonstrated. Modified polymers can be prepared by reacting a functional group-containing modifier at the living end of a polymer obtained using an organolithium compound as a polymerization catalyst to add a functional group-containing atomic group. The functional group-containing atomic group is bonded to one or more polymer chain ends of the polymer.

Examples of functional groups of the functional group-containing atomic group bonded to the modified polymer include hydroxyl groups, carbonyl groups, thiocarbonyl groups, acid halide groups, acid anhydride groups, carboxyl groups, thiocarboxylic acid groups, aldehyde groups, thioaldehyde groups, carboxylate groups, amido groups , Sulfonic acid group, sulfonate group, phosphoric acid group, phosphate group, amino group, imino group, cyano group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silane One or more functional groups selected from the group consisting of oligo groups, alkoxysilane groups, tin halide groups, alkoxytin groups, phenyltin groups and the like. Among the functional groups mentioned above, hydroxyl groups, epoxy groups, amino groups, imino groups, silanol groups and alkoxysilane groups are particularly preferred.

Preferred examples of the atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group and an alkoxysilane group include those represented by the formulas selected from the group consisting of the following formulas (1) to (14) One or more species are included:

[In the formulas (1) to (14), N represents a nitrogen atom; Si represents a silicon atom; O represents an oxygen atom; C represents a carbon atom; H represents a hydrogen atom; R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and the hydrocarbon group has a hydroxyl group, an epoxy group, an amino group, and an imino group (having a hydrocarbon group having 1 to 24 carbon atoms) as desired. , May have one or more functional groups selected from the group consisting of silanol groups and alkoxysilane groups having 1 to 24 carbon atoms; Each R ³ independently represents a divalent hydrocarbon group having 1 to 48 carbon atoms, and as desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group (having a hydrocarbon group having 1 to 24 carbon atoms), a silane May have one or more functional groups selected from the group consisting of an oligo group and an alkoxysilane group having 1 to 24 carbon atoms; Each R ⁴ independently represents a hydrocarbon group having 1 to 24 carbon atoms.

In the present invention, as the modifier that can be used to bind the above-described functional group-containing atomic group to the modified polymer, known compounds having the aforementioned functional groups and / or known compounds capable of forming the same can be used. For example, the terminal modification treatment agent described in JP-B-04-39495 (corresponding to U.S. Patent No. 5,115,035) can be used. Specific examples thereof include the following.

Examples of the modifier having a functional group of the above formulas (1) to (6) include tetraglycidylmethylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenyl Rendiamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl ortho toluidine, N- (1,3-dibutylbutylidene) -3- (triethoxysilyl) -1 -Propanamine, 4-di (β-trimethoxysilylethyl) aminostyrene, 4-di (β-triethoxysilylethyl) aminostyrene, 4-di (γ-trimethoxysilylpropyl) aminostyrene and 4 -Di (γ-triethoxysilylpropyl) aminostyrene.

Examples of modifiers having a functional group of formula (7) above include cyclic lactones such as ε-caprolactone, δ-valerolactone, butyrolactone, γ-caprolactone and γ-valerolactone.

Examples of the modifier having a functional group of formula (8) described above include 4-methoxybenzophenone, 4-ethoxybenzophenone, 4,4'-bis (methoxy) benzophenone, 4,4'-bis (ethoxy ) Benzophenone, γ-glycidoxyethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

Examples of modifiers having functional groups of the formulas (9) and (10) described above include γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltripropoxysilane And γ-glycidoxypropyltributoxysilane.

Examples of the modifier having a functional group of the formula (11) described above include 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone.

Examples of modifiers having a functional group of formula (12) above include N, N'-dimethylpropyleneurea and N-methylpyrrolidone.

In addition, modified polymers having atomic groups having the functional groups of the formulas (13) and (14) described above are obtained by hydrogenating non-hydrogenated polymers having the atomic groups containing the functional groups of the formulas (11) and (12), respectively. .

The hydrogenation products of the modified polymers used in component (2) of the present invention can also be prepared by hydrogenation after modification of the polymer or by modification after hydrogenation of the polymer. For example, in the case of hydrogenation after modification of the polymer, the living end of the polymer obtained using the organolithium compound as the polymerization catalyst and the aforementioned modifier are reacted to obtain a modified polymer, and the resulting modified polymer is hydrogenated to undergo hydrogenation modification. Obtain a polymer.

In addition, another method for obtaining a modified polymer used in component (2) of the present invention is to react an organic alkali metal compound such as an organolithium compound with a polymer (metal chloride reaction) to obtain a polymer to which an organic alkali metal compound is added, as mentioned above. A method of reacting a modifier with it is included. In this case, it is also possible to obtain a hydrogenation modified polymer by carrying out a metal chloride reaction after the hydrogenation product of the polymer and reacting the aforementioned modifier.

Depending on the type of modifier, hydroxyl groups, amino groups and the like may sometimes be in the form of organometallic salts in the step of reacting the modifier. In such a case, the salt may be treated with a compound having water or active hydrogen such as alcohol to form hydroxy group, amino group and the like.

In the present invention, the reaction pressure for carrying out the reforming reaction is not particularly limited, but is usually 0.2 to 2 MPa, preferably 0.3 to 1 MPa. Reaction temperature becomes like this. Preferably it is in the range of 0-150 degreeC, More preferably, it is in the range of 20-120 degreeC, More preferably, it is in the range of 50-100 degreeC. The time required for the reforming reaction generally depends on the reaction temperature at the time of preparation, but is in the range of 1 second to 10 hours, preferably in the range of 1 second to 3 hours.

In the present invention, after reacting the modifier with the polymer, the unmodified polymer may be present as a mixture in the modified polymer. The amount of unmodified polymer present as a mixture in the modified polymer is preferably 70% by weight or less, more preferably 60% by weight or less and even more preferably 50% by weight or less, based on the weight of the modified polymer.

In the present invention, the hydrogenation product of the modified polymer is obtained by hydrogenating the obtained modified polymer. The hydrogenation catalyst is not particularly limited, and is commonly known, (1) a carrier heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, Ru, and the like are carried to carbon, silica, alumina, diatomaceous earth, and the like, (2) transition metal salts such as Organic acid salts such as Ni, Co, Fe, Cr, or acetylacetone salts and so-called Ziegler type hydrogenation catalysts with reducing agents such as organoaluminum, and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes such as Ti, Ru, Rh, Zr, etc. Organometallic compounds of are used.

As specific hydrogenation catalysts, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-01-53851 and JP-B-2 The hydrogenation catalyst described in -9041 can be used. Preferred examples of hydrogenation catalysts include titanocene compounds and / or mixtures of these and reducing organometallic compounds. As the titanocene compound, the compound described in JP-A-8-109219 can be used. Specific examples thereof include compounds having one or more ligands having a (substituted) cyclopentadienyl skeleton such as biscyclopentadienyltitanium dichloride or monopentamethylcyclopentadienyltitanium trichloride, indenyl skeleton or fluorenyl skeleton. Branches include compounds having one or more ligands. Further, the reduced organometallic compound includes organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, organozinc compounds and the like.

The hydrogenation reaction is preferably performed at a temperature range of 0 to 200 ° C, more preferably at a temperature range of 30 to 150 ° C. The hydrogen pressure used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, even more preferably 0.3 to 5 MPa. In addition, the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. Any of batch processes, continuous processes, and combinations thereof can be used for the hydrogenation reaction.

In the hydrogenation product of the modified polymer used in the present invention, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene-based monomer units can be freely selected according to the purpose, and is not particularly limited. When a hydrogenated product of a modified polymer having good thermal stability and weather resistance is obtained, at least 70%, preferably at least 80% and more preferably at least 90% of unsaturated double bonds are hydrogenated based on the conjugated diene-based monomer units in the modified polymer. It is recommended. It is also possible to hydrogenate only part of it. When only part of the hydrogenation is desired, it is desirable to adjust the hydrogenation ratio to 10% to less than 70% or 15% to less than 65%, 20% to less than 60% as desired. In addition, in obtaining a rubber composition having excellent thermal stability, the hydrogenation ratio of the vinyl bonds is preferably 85% or more, more preferably 90% or more, even more preferably 95% or more based on the conjugated diene monomer before hydrogenation. It is recommended. As used herein, the hydrogenation ratio of vinyl bonds refers to the ratio of hydrogenated vinyl bonds to vinyl bonds based on conjugated diene-based monomers prior to hydrogenation, incorporated into the modified polymer. There is no particular restriction on the hydrogenation ratio of aromatic double bonds based on vinyl aromatic hydrocarbons in the modified random copolymer or modified block copolymer, but is preferably at most 50%, more preferably at most 30%, even more preferably at 20% The following is recommended. The hydrogenation ratio can be known using a nuclear magnetic resonance apparatus (NNR).

Next, in the present invention, it is also possible to use a secondary modified polymer which is a reaction product of a compound (4) having a reactivity with a functional group bonded to the modified polymer used in the preparation of the master batch. The secondary modified polymer is obtained by reacting a secondary modifier with the modified polymer of the present invention as compound (4), and the secondary modifier is a compound having a functional group having reactivity with the functional group of the modified polymer.

Preferred examples of the functional group of the secondary modifier as compound (4) include at least one member selected from carboxyl group, acid anhydride group, isocyanate group, epoxy group, silanol group and alkoxysilane group. Particular preference is given to secondary modifiers having at least two functional groups mentioned above. However, when the functional group is an acid anhydride group, secondary modifiers having only one acid anhydride group are also particularly preferred. When the secondary modifier is reacted with the modifying polymer, the amount of the secondary modifier is usually 0.3 to 10 moles, preferably 0.4 to 5 moles, more preferably 0.5 to 4 moles per equivalent of functional groups bonded to the modifying polymer.

The method of reacting a secondary modifier with a modified polymer is not specifically limited, A well-known method can be used. Examples thereof include a melt kneading method described later, a method of dissolving or dispersing individual components in a solvent or the like, and reacting the mixture. In the method in which the individual components are dissolved or dispersed in a solvent or the like and reacted, the solvent is not particularly limited as long as the individual components are dissolved or dispersed. Halogen-containing solvents, ester solvents, ether solvents and the like, as well as hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons can be used. In such a process, the temperature at which the secondary modifier is reacted with the modifying polymer is usually -10 to 150 ° C, preferably 30 to 120 ° C. The time required for the reaction generally depends on the reaction temperature at the time of manufacture, but is 3 hours or less, preferably several seconds to 1 hour. A particularly preferred method is a method in which a secondary modified polymer is obtained by adding and reacting a secondary modifier to a solution of the prepared modified polymer.

Specific examples of secondary modifiers are described below. Examples of carboxyl group-containing secondary modifiers include maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carvalyl acid, cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid. Aliphatic carboxylic acid; And aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid.

Examples of acid anhydride group-containing secondary modifiers include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzene Tetracarboxylic dianhydride and 5- (2,5-dioxytetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride.

Examples of isocyanate group-containing secondary modifiers include toluylene diisocyanate, diphenylmethane diisocyanate, polyfunctional aromatic isocyanates (ie, compounds in which three or more isocyanate groups are bonded to an aromatic ring) and the like.

Examples of epoxy group-containing secondary modifiers include tetraglycidyl-1,3-bisaminomethyl-cyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene Glycol diglycidyl, diglycidyl terephthalate acrylate, and the like.

Examples of silanol group-containing secondary modifiers include hydrolysates of the aforementioned alkoxysilane compounds described as modifiers used to obtain modified polymers, and the like.

Examples of alkoxysilane group-containing secondary modifiers include bis- (3-triethoxysilylpropyl) tetrasulfane, bis- (3-triethoxysilylpropyl) disulfane and ethoxysiloxane oligomers.

In addition, functional oligomers having reactivity can also be used as secondary modifiers. The functional group of the functional oligomer is not particularly limited as long as it is a functional group having reactivity with a functional group bonded to the modified polymer. Preferred examples of functional oligomers include functional oligomers having one or more functional groups selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, isocyanate groups, epoxy groups, silanol groups and alkoxysilane groups. The number average molecular weight of these functional oligomers is usually less than 300 to 30,000, preferably less than 500 to 15,000, more preferably less than 1,000 to 20,000. Specific examples of functional oligomers include butadiene oligomers having at least one functional group or hydrogenation products thereof, isoprene oligomers having at least one functional group mentioned above or hydrogenated products thereof, ethylene oligomers having at least one functional group mentioned above, Propylene oligomers having one or more functional groups, ethylene oxide oligomers, propylene oxide oligomers, ethylene oxide-propylene oxide oligomers, styrene-maleic anhydride oligomers, saponified products of ethylene-vinyl acetate copolymers, and the like. .

Particularly preferred examples of secondary modifiers in the present invention are carboxylic acids having two or more carboxyl groups or acid anhydrides thereof and acid anhydride groups, isocyanate groups, epoxy groups, silanol groups or alkoxysilane groups. Specific examples thereof include maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, bis -(3-tri-ethoxysilylpropyl) -tetrasulfane, styrene-maleic anhydride cooligomers and the like.

In addition, when preparing the master batch of component (2), in addition to the modified polymer and the inorganic filler, a secondary modifier as compound (4) mentioned above can be added. The amount of secondary modifier is in the range of 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the modified polymer.

The weight average molecular weight of the modified polymer of the secondary modified polymer used in component (2) of the present invention is preferably 30,000 or more in terms of mechanical strength and wear resistance of the rubber composition, 1,200,000 or less, more preferably 50,000 in view of workability. It is in the range of from 1,000,000, even more preferably in the range of 100,000 to 800,000. The weight average molecular weight of the modified polymer is measured by gel permeation chromatography (GPC), and the peak molecular weight of the chromatogram can be measured using a calibration curve obtained from commercial standard polystyrene measurements (created using the peak molecular weight of standard polystyrene). .

If necessary, the catalyst residue can be removed from the solution of the modified polymer obtained as described above, and the modified polymer can be separated from the solution. Solvent separation methods include, for example, a method of recovering a polymer by precipitating the polymer by adding a polar solvent such as acetone or an alcohol, which acts as a poor solvent to the copolymer, after polymerization or hydrogenation; A method of recovering the polymer by injecting the modified polymer solution into boiling water with stirring and removing the solvent by steam degassing; And a method of directly heating the polymer solution to remove the solvent by distillation. On the other hand, stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers can be added to the modified polymers or hydrogenation products thereof used in the present invention.

In the present invention, the inorganic filler used as a raw material in the master batch of the component (2) or the inorganic filler of the component (3) is synthetic silica, kaolin, mica, talc, clay, montmorillonite, prepared by natural silica, wet or dry method, Zeolites, natural silicates, synthetic silicates such as calcium silicate and aluminum silicate, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide and barium hydroxide, metal oxides such as alumina, titanium oxide, magnesium oxide and zinc oxide, metal carbonates such as hard precipitated calcium carbonate, Heavy calcium carbonate, various surface-treated calcium carbonates and magnesium carbonates, metal sulfates such as barium sulfate, magnesium sulfate and calcium sulfate, metal powders such as aluminum, bronze, carbon black and the like. Preferred examples of fillers include silica-based inorganic fillers, metal oxides, metal hydroxides and carbon. The aforementioned inorganic fillers may be used alone or in combination of two or more thereof.

Silica-based inorganic fillers mean solid particles whose structural units consist mainly of the formula SiO ₂ , and for example, silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolites, inorganic fibrous materials such as glass fibers, etc. may be used. Can be. It is also possible to use surface-hydrogenated silica-based fillers or mixtures of silica-based inorganic fillers with inorganic fillers other than silica-based.

In the present invention, silica is preferred. As silica, what is called dry process white carbon, a wet process white carbon, a synthetic silicate type white carbon, or colloidal silica can be used. These are preferably those having a particle size of 0.01 to 150 μm. Further, in the composition of the present invention, in order to disperse the silica in the composition so as to sufficiently exhibit the silica addition effect, the average size of the dispersed particles is preferably 0.05 to 1 m, more preferably 0.05 to 0.5 m.

Next, a metal oxide structural units is mainly refers to solid particles consisting of the formula M _x O _y (M is a metal atom, x and y are an integer of 1 to 6 respectively), and for example, alumina, titanium oxide , Magnesium oxide, zinc oxide and the like can be used. In addition, the metal hydroxides used in the present invention are hydrated inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide silicate, magnesium hydroxide silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide or inorganic metal compounds such as It is a hydrate of tin oxide or borax. Magnesium hydroxide and aluminum hydroxide are particularly preferred.

As the carbon black, each class of carbon black such as FT, SRF, FEF, HAF, ISAF or SAF can be used, the carbon black having a nitrogen adsorption specific surface area of 50 mg or more and a DBP oil absorption of 80 ml / 100 g. This is preferable.

In the present invention, the amount of the inorganic filler used in the preparation of the master batch of component (2) is 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight based on 100 parts by weight of the modified polymer. It is the range of weight part. When the amount of the inorganic filler exceeds 300 parts by weight, the dispersibility of the inorganic filler is poor, and the workability of the master batch is deteriorated. If it is less than 5 weight part, the adhesiveness which is an effect of this invention is inferior.

Further, in the present invention, the compounding amount of the inorganic filler of component (3) is 0.1 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the rubbery polymer of component (1). It is wealth. When the amount of the inorganic filler blended exceeds 150 parts by weight, the dispersibility of the inorganic filler is poor, and workability and mechanical strength deteriorate. Therefore, this is not desirable.

When using a silica type inorganic filler for manufacture of the rubber composition for threading of this invention, a silane coupling agent can be used. The silane coupling agent is intended to close the interaction between the rubbery polymer and the inorganic filler and has a group having affinity or binding ability to both the rubbery polymer and the inorganic filler. Specific examples thereof include bis- [3- (triethoxysilyl) propyl] tetrasulfide, bis- [3- (triethoxysilyl) propyl] disulfide, bis- [2- (triethoxysilyl) ethyl] Tetrasulfide, 3-mercaptopropyl-trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.

Preferred silane coupling agents are those having polysulfides and alkoxysilanes at which two or more sulfur atoms are bonded together, examples of which include bis- [3- (triethoxysilyl) propyl] tetrasulfide, bis- [3 -(Triethoxysilyl) propyl] disulfide and the like. The compounding amount of the silane coupling agent is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the reinforcing filler.

In the master batch of component (2) of the present invention, the use of modified polymers with effective binding of functional groups having high affinity for inorganic fillers results in chemical bonding or physical interaction between functional groups present on the surface of the inorganic fillers and the modified polymers. Actions such as hydrogen bonds appear, whereby a rubber composition for footwear excellent in tear strength, wear resistance and adhesion can be obtained.

The master batch manufacturing method as component (2) of this invention is not specifically limited, A well-known method can be used. For example, kneading methods using common kneaders such as banbury mixers, single screw extruders, twin screw extruders, cokneaders, multi-screw extruders or rolls, dissolving and mixing the individual components, and then heating to solvent The method of removing it is used. The preferred method is to knead the individual components using a Banbury mixer or co-kneader.

In the preparation of the master batch, there is no restriction in the order of addition of the modified polymer and the inorganic filler, and the method of kneading after supplying all the components to the kneader at once, the method of kneading after dividing the individual components two or more times and feeding the kneader, the reforming After supplying the polymer to the kneader, kneading, and then adding an inorganic filler, kneading, supplying the inorganic filler to the kneader, kneading, then adding a modified polymer, kneading, then the inorganic filler After continuously supplying to a kneader, the method of kneading | mixing, etc. can be used.

The kneading temperature in the case of producing the master batch is generally preferably 80 to 300 ° C. in order to enhance the deterioration of the modified polymer and the interaction between the modified polymer and the inorganic filler to obtain a master batch having good dispersibility of the inorganic filler. More preferably, it is 130-250 degreeC, More preferably, it is 150-220 degreeC. In addition, the kneading time is generally 0.2 to 60 minutes, more preferably 0.5 to 30 minutes, even more preferably 1 to 1 in terms of dispersibility of the inorganic filler, productivity of the master batch, deterioration of the modified polymer, and the like. 20 minutes.

A particularly preferred method is a method of preparing the master batch by feeding the inorganic filler to the kneader in advance and then kneading and then adding the modified polymer and then kneading the inorganic filler into the kneader by dividing the inorganic filler two or more times, and then modifying the polymer. And a method of preparing a master batch by kneading the inorganic filler.

As a method of dividing the inorganic filler into two or more times and supplying it to the kneader, in consideration of the complexity of the master batch manufacturing process, it is preferable to add the inorganic filler in two to ten portions, and in particular, the inorganic filler is added in two to five portions. The method is preferred. Specifically, 20 to 80% by weight, preferably 30 to 80% by weight, more preferably 40 to 80% by weight of the inorganic filler is previously added to the kneader, and then 1 second to 60 minutes, preferably 0.5 to Kneading for 30 minutes, more preferably for a kneading time ranging from 1 to 20 minutes, and then adding the modified polymer, then 1 second to 60 minutes, preferably 20 seconds to 30 minutes, more preferably 1 to 20 minutes Kneading for a kneading time in the range, followed by addition of the remaining inorganic filler, followed by kneading for a kneading time in the range of 1 second to 60 minutes, preferably 0.5 to 30 minutes, more preferably 1 to 20 minutes. There is a method of manufacturing. As another preferred method, the inorganic filler is pre-fed to the kneader with the whole quantity, followed by kneading for a kneading time ranging from 1 second to 60 minutes, preferably from 0.5 to 30 minutes, more preferably from 1 to 20 minutes, and then to the modified polymer. After the addition, there is a method of preparing a master batch by kneading for a kneading time in the range of 1 second to 60 minutes, preferably 0.5 to 30 minutes, more preferably 1 to 20 minutes.

In preparing the master batch in a particularly preferred shape, at least 20% by weight of at least 20% by weight of the inorganic filler in the range of 50 to 300 ° C, preferably 70 to 250 ° C, more preferably 100 to 200 ° C It is most important to prepare the master batch by feeding the kneader in advance and then kneading with the addition of the remaining ingredients.

The rubber composition for shoes of the present invention is a rubber composition comprising a rubbery polymer (component 1) and a master batch (component 2), or a rubbery polymer (component 1), a master batch (component 2) and an inorganic filler (component 3). The amount of the master batch is in the range of 1 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the rubbery polymer (component 1).

The manufacturing method of the rubber composition for shoes of this invention is not specifically limited, A well-known method can be used. For example, a kneading method using a general kneader such as a Banbury mixer, a single screw extruder, a twin screw extruder, a co-kneader or a multi screw extruder is used.

In addition, when manufacturing the rubber composition for footwear of the present invention, there is no restriction on the order of addition of the individual components, and the method of kneading after supplying the component (1), the component (2) and the component (3) all at once to the kneader, and After mixing arbitrary components in advance, the method of adding remaining components can be used. The kneading temperature is preferably 50 to 300 ° C, more preferably 70 to 250 ° C, even more preferably 100 to 200 ° C in terms of thermal degradation of the rubbery polymer and the modified polymer. Further, the kneading time is generally 0.2 to 60 minutes, more preferably 0.5 to 30 minutes, even more preferably in terms of dispersibility of the inorganic filler, productivity of the rubber composition, deterioration of the modified polymer and the rubbery polymer, and the like. Is 1 to 20 minutes.

The rubber composition for footwear of the present invention is characterized by using a master batch having excellent dispersibility of the inorganic filler obtained by kneading the modified polymer and the inorganic filler by the specific manufacturing method described above. Compared to the rubber composition for shoes obtained by kneading the rubbery polymer or the modified polymer and the inorganic filler, which has been performed so far, the dispersibility of the inorganic filler can be improved to obtain a rubber composition for shoes having excellent wear resistance and adhesion. The dispersibility of the inorganic filler in the rubber composition can be confirmed using a transmission electron microscope, a scanning probe microscope, or the like.

In the present invention, any other additives may be blended if necessary. The type of the additive is not particularly limited as long as the additive is generally used in the blending of the rubbery polymer. Examples thereof include zinc white, stearic acid, vulcanizing aids, anti-aging agents, processing aids, lubricants such as behenic acid, zinc stearate, calcium stearate, magnesium stearate or ethylene bis stearamide, mold release agents, paraffinic processing oils and naphthenic processing oils. , Softeners / plasticizers such as aromatic processing oils, paraffins, organic polysiloxanes or mineral oils, antioxidants such as hindered phenolic antioxidants or phosphorus thermal stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, Antistatic agents, organic fibers, glass fibers, reinforcing agents such as carbon fibers or metal whiskers, colorants, other additives or mixtures thereof, and described in "Chemicals for Blending in Rubber / Plastics" (edited by Rubber Digest, Co., Ltd.) Things are included.

Although this invention is demonstrated in more detail with reference to an Example, it should not be interpreted that this invention is limited by that.

[Analysis Method of Styrene-Butadiene Rubber]

(1) styrene bond amount

Using an ultraviolet spectrophotometer (V-520 UV; manufactured by JASCO Corporation), the measurement was made in comparison with the UV absorption intensity of standard polystyrene.

(2) 1,2-vinyl bond in butadiene

It measured using the ultraviolet spectrophotometer (V-520UV; JASCO Corporation make), and determined by Hampton method.

(3) molecular weight

It was measured by GPC (instrument: LC10; manufactured by Shimadzu Corporation, column: Shimpac GPC8O5 + GPC8O4 + GPC8O4 + GPC8O3; manufactured by Shimadzu Corporation). Tetrahydrofuran was used as a solvent and it measured under the measurement conditions of 35 degreeC. Molecular weight is the weight average molecular weight measured using the calibration curve (made using the peak molecular weight of standard polystyrene) obtained from a commercial standard polystyrene measurement.

(4) ratio of unmodified polymer

A sample solution was prepared by dissolving 10 mg of modified polymer and 10 mg of low molecular weight internal standard polystyrene having a weight average molecular weight of 8000 in 20 ml of tetrahydrofuran. In the sample solution, GPC measurements were performed in the same manner as in (3) described above, and the ratio (i) of the modified polymer to standard polystyrene was determined from the chromatogram obtained. In addition, the chromatogram was obtained by performing the GPC measurement in the same manner as in (3) described above, except that the Zorbax column (silica-based gel filler), a column manufactured by DuPont, USA, was used for the aforementioned sample solution. Got it. The modified polymer was adsorbed on the GPC column using silica-based gel as filler, but the unmodified polymer was not adsorbed on the column. Thus, the ratio (ii) of the unmodified polymer to standard polystyrene can be obtained from the chromatogram obtained. From the aforementioned ratios (i) and (ii), the ratio (%) of the modified polymer in the copolymer after the modification reaction was calculated by the following formula: (1-ratio (ii) / ratio (i)) x 100.

[Measurement of Physical Properties of Rubber Polymer Composition]

(1) tensile test

It measures in 23 degreeC constant temperature room based on JISK6251.

(2) tear test

It measures in 23 degreeC constant temperature room according to JISK6252.

(3) hardness measurement

Using a ASKER hardness tester manufactured by Koubunshi Keiki Co., Ltd, Type C, measured in a constant temperature room at 23 ℃.

(4) transparency

Nippon Denshoku Industries Co., Ltd. The turbidity value and total light transmittance of the plate sample of thickness 5mm were measured using the turbidimeter, Type NDH-1001DP manufactured by.

(5) wear resistance index

The loss of wear of the sample was measured with an Akron type tester, and the index determined by the following equation was determined as the wear resistance index.

Index = [(Abrasion Reduction of Sample) / (Abrasion Reduction of Standard Sample)] × 100

(6) adhesive test

Peeling strength after adhering the rubber composition to the adhesive surface (leather, nylon or EVA) was measured using an aqueous primer (AQUACE PR-503) and an aqueous adhesive (AQUACE W-06).

[Production of diene polymer]

(Manufacture of SBR-A)

The atmosphere was replaced with nitrogen gas, and 5.5 kg of purified cyclohexane, 0.40 kg of styrene monomer and 0.45 kg of 1,3-butadiene were placed in a 10-liter autoclave equipped with a stirrer, and the temperature was adjusted to 60 ° C while stirring. Uploaded. Then, 32 g of tetrahydrofuran and 0.83 g of n-butyllithium were added to initiate the polymerization reaction. 0.15 kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes from the middle of the polymerization to the maximum temperature of 92 ° C. After 1 minute after the maximum polymerization temperature, tetraglycidyl-1,3-bisaminomethylcyclohexane is added in an amount of 0.38 mol based on n-butyllithium used as the polymerization initiator, and reacted to obtain SBR-A. Got it. Subsequently, 2,6-di-tert-butyl-4-methylphenol was added to the polymer solution as a stabilizer in an amount of 0.5 parts by weight per 100 parts by weight of rubber, followed by desolvation and drying with a drum dryer. As a result of analysis of the resulting polymer, the styrene content was 40% by weight, and the vinyl bond amount of the butadiene portion was 33% by weight. According to the analysis of the amount of block styrene, there was no styrene block. Furthermore, the weight average molecular weight was 493,000, and the modification rate was 71%.

(Manufacture of SBR-B)

The atmosphere was replaced with nitrogen gas, and 5.5 kg of purified cyclohexane, 0.40 kg of styrene monomer and 0.45 kg of 1,3-butadiene were placed in a 10-liter autoclave equipped with a stirrer, and the temperature was adjusted to 60 ° C while stirring. Uploaded. Then, 32 g of tetrahydrofuran and 0.83 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. 0.15 kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes from the middle of the polymerization to the maximum temperature of 92 ° C. 1 minute after the maximum polymerization temperature, 1,3-dimethyl-2-imidazolidinone was added in an amount of 1 mol based on n-butyllithium used as the polymerization initiator, and reacted to obtain SBR-B. Subsequently, 2,6-di-tert-butyl-4-methylphenol was added to the polymer solution as a stabilizer in an amount of 0.5 parts by weight per 100 parts by weight of rubber, followed by desolvation and drying with a drum dryer. As a result of analysis of the resulting polymer, the styrene content was 40% by weight, and the vinyl bond amount of the butadiene portion was 33% by weight. According to the analysis of the amount of block styrene, there was no styrene block. Furthermore, the weight average molecular weight was 491,000 and the modification rate was 80%.

(Manufacture of SBR-C)

After using 180 g of SBR-B obtained above and blending 0.1 g of maleic anhydride as a secondary modifier, an internal kneader equipped with a temperature controller under a condition of a kneading temperature of 100 ° C. and a kneading time of 3 minutes ( Internal volume: 0.3 liters) to knead to obtain a secondary modified polymer.

(Manufacture of SBR-D)

The atmosphere was replaced with nitrogen gas, and 5.5 kg of purified cyclohexane, 0.40 kg of styrene monomer and 0.45 kg of 1,3-butadiene were placed in a 10-liter autoclave equipped with a stirrer, and the temperature was adjusted to 60 ° C while stirring. Uploaded. Then, 32 g of tetrahydrofuran and 0.83 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. 0.15 kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes from the middle of the polymerization to the maximum temperature of 89 ° C. Three minutes after the maximum temperature reached 89 ° C., the polymer solution was withdrawn and deactivated with 10-fold molar excess of water relative to n-butyllithium to obtain SBR-C. Subsequently, 2,6-di-tert-butyl-4-methylphenol was added to the polymer solution as a stabilizer in an amount of 0.5 parts by weight per 100 parts by weight of rubber, followed by desolvation and drying with a drum dryer. As a result of analysis of the resulting polymer, the styrene content was 40% by weight, and the vinyl bond amount of the butadiene portion was 33% by weight. According to the analysis of the amount of block styrene, there was no styrene block. In addition, the weight average molecular weight was 485,000.

[Manufacture of Master Batch]

(MB-1)

Using an internal kneader (internal capacity: 1.7 liters) equipped with a temperature controller using circulating water from the outside, 25 parts of silica were first fed into the kneader, followed by a filling rate of 65% and a rotational speed of 66/77 rpm. It was kneaded for 4 minutes under conditions. 75 parts of polymer and 0.15 parts of stearic acid were then fed into the kneader and kneading continued for 4 minutes. The temperature of the rubber composition after discharging was 170 ° C. After cooling, kneading was again performed using an open roll set at 50 ° C. to produce a polymer / silica master batch. The formulation is shown in Table 1.

(MB-2, 3, 4, and 6)

Using an internal kneader (internal capacity: 1.7 liters) equipped with a temperature controller using circulating water from the outside, 12.5 parts of silica was first fed into the kneader, followed by a filling rate of 65% and a rotational speed of 66/77 rpm. It was kneaded for 4 minutes under conditions. 75 parts of polymer and 0.15 parts of stearic acid were then fed into the kneader and then kneaded for 3 minutes. Then 12.5 parts of silica was further fed into the kneader and kneading continued for 3 minutes. The temperature of the rubber composition after discharging was 170 ° C. After cooling, kneading was again performed using an open roll set at 50 ° C. to produce a polymer / silica master batch. The formulation is shown in Table 1.

(MB-5)

25 parts of silica, 75 parts of polymer and 0.15 parts of stearic acid were fed into the kneader using an internal kneader (inner capacity: 1.7 liters) equipped with a temperature controller using circulating water from the outside, with a filling rate of 65% and Kneading was continued for 5 minutes under the condition of sequential rotational speed 66/77 rpm. The temperature of the rubber composition after discharging was 170 ° C. After cooling, kneading was again performed using an open roll set at 50 ° C. to produce a polymer / silica master batch. The formulation is shown in Table 1.

[Examples 1 to 5]

Using an internal kneader (internal capacity: 1.7 liters) equipped with a temperature controller using externally circulating water, the individual components were fed into the kneader in one mass according to each formulation shown in Table 2, and the filling rate 65 % And kneaded under conditions of a sequential rotational speed of 66/77 rpm to obtain a rubber composition. The temperature after discharge was 161 ° C. Sulfur and a vulcanization accelerator were added to the rubber composition thus obtained, and the mixture was kneaded using an open roll set at 70 ° C. Subsequently, vulcanization was performed at 160 ° C. for 20 minutes to prepare a test piece. Physical properties of the vulcanizate are shown in Table 2. It is shown that the tear strength and wear resistance of rubber compositions prepared using the modified polymers and silica master batches of the present invention are excellent.

[Comparative Examples 1 and 2]

In the same manner as in Example 1, according to each formulation shown in Table 2, the individual components were fed in a mass into the kneader and kneaded to obtain a rubber polymer composition. The temperature after discharge was 160 ° C. Sulfur and a vulcanization accelerator were added to the rubber composition thus obtained, and the mixture was kneaded using an open roll set at 70 ° C. Subsequently, vulcanization was performed at 160 ° C. for 20 minutes to prepare a test piece. Physical properties of the vulcanizate are shown in Table 2.

[Examples 6 to 12]

Using an internal kneader (internal capacity: 1.7 liters) equipped with a temperature controller using circulating water from the outside, the individual components were fed into the kneader in one mass according to each formulation shown in Table 3, and the filling rate 65 % And kneaded under conditions of a sequential rotational speed of 66/77 rpm to obtain a rubber composition. The temperature after discharge was 160 ° C. Sulfur and a vulcanization accelerator were added to the rubber composition thus obtained, and the mixture was kneaded using an open roll set at 70 ° C. Subsequently, vulcanization was performed at 160 ° C. for 20 minutes to prepare a test piece. Physical properties of the vulcanizate are shown in Table 3. It is shown that the adhesive composition of the rubber composition prepared using the modified polymer of the present invention and the silica master batch is excellent.

[Comparative Examples 3 and 4]

In the same manner as in Example 6, in accordance with each formulation shown in Table 3, the individual components were fed in a mass into the kneader and kneaded to obtain a rubber polymer composition. Sulfur and a vulcanization accelerator were added to the rubber composition thus obtained, and the mixture was kneaded using an open roll set at 70 ° C. Subsequently, vulcanization was performed at 160 ° C. for 20 minutes to prepare a test piece.

While the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may occur without departing from the spirit and scope of the invention.

This invention is based on Japanese Patent Application No. 2003-369255 for which it applied on October 29, 2003, The content is taken in here as a reference.

The rubber composition for shoes of the present invention is excellent in tear strength and wear resistance, and also excellent in adhesion to nylon, leather and EVA, which are shoes materials. Due to these features, the compositions of the present invention are very effective materials for various shoe sole materials. Furthermore, it can be processed into molded articles of various shapes and can be used in automobile parts (automobile interior materials and automotive exterior materials), various containers such as food packaging containers, household appliances, medical instrument fields, industrial fields, toys and the like.

Claims (16)

A rubber composition for footwear, comprising: Component (1): 100 parts by weight of a rubbery polymer; And Component (2): 100 weights of one or more modified polymers selected from conjugated diene-based polymers, copolymers of conjugated diene-based monomers and vinyl aromatic hydrocarbons, or modified polymers of hydrogenation products thereof, each having one or more functional group-containing atom groups bound thereto 1 to 150 parts by weight of a master batch obtained by kneading parts and 5 to 300 parts by weight of an inorganic filler. 2. The shoe according to claim 1, wherein the component (2) is a master batch obtained by kneading after pre-feeding 5 to 300 parts by weight of the inorganic filler into the kneader, followed by kneading and then adding the modified polymer. Rubber composition. 2. The rubber composition for shoes according to claim 1, wherein the component (2) is a master batch obtained by sequentially kneading 5 to 300 parts by weight of an inorganic filler into a kneader two times and then kneading them sequentially. 2. The component (2) according to claim 1, wherein component (2) is pre-fed 20 to 80% by weight of an inorganic filler into the kneader, followed by kneading, followed by addition of a modified polymer, followed by kneading, and further residual amount of the inorganic filler The rubber composition for shoes which is a master batch obtained by kneading after adding. 2. The rubber composition for footwear according to claim 1, further comprising 0.1 to 150 parts by weight of inorganic filler as component (3). The rubber composition for footwear according to claim 1, wherein the functional group-containing atomic group of the modified polymer is an atomic group having at least one functional group selected from the group consisting of hydroxyl group, epoxy group, amino group, imino group, silanol group and alkoxysilane group. The rubber composition for footwear according to claim 1, wherein at least one atomic group selected from formulas (1) to (14) is bonded to the modified polymer:

[In the above-mentioned formulas (1) to (14), N represents a nitrogen atom; Si represents a silicon atom; O represents an oxygen atom; C represents a carbon atom; H represents a hydrogen atom; R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and the hydrocarbon groups are each independently, as desired, a hydroxyl group, an epoxy group, an amino group, an imino group (a hydrocarbon having 1 to 24 carbon atoms). Group), a silanol group and an alkoxysilane group having 1 to 24 carbon atoms; Each R ³ independently represents a divalent hydrocarbon group having 1 to 48 carbon atoms, and as desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group (having a hydrocarbon group having 1 to 24 carbon atoms), a silane May have one or more functional groups selected from the group consisting of an oligo group and an alkoxysilane group having 1 to 24 carbon atoms; Each R ⁴ independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. The method according to claim 1, wherein the component (2), when kneading the modified polymer and the inorganic filler, contains 0.01 to 20 parts by weight of a compound (4) having a reactivity with the functional group bonded to the modified polymer, based on 100 parts by weight of the modified polymer. A rubber composition for footwear, which is a master batch obtained by further addition in amounts. The compound (4) according to claim 1, wherein the component (2) is a compound (4) having a reactivity with a functional group bonded to the modified polymer to the kneaded product of the modified polymer and the inorganic filler, based on 100 parts by weight of the modified polymer, from 0.01 to 20% by weight. A rubber composition for footwear, which is a master batch obtained by further addition in negative amounts. The modified polymer used in component (2) according to claim 1, wherein compound (4) having a reactivity with a functional group bonded to the modified polymer is reacted in an amount of 0.3 to 10 moles per equivalent of functional group bonded to the modified polymer. A rubber composition for footwear, which is a modified polymer obtained by the following. The rubber composition for shoes according to claim 8 or 9, wherein the component (4) is a compound having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. A process for producing a rubber composition for shoes, comprising the steps of kneading: Component (1): 100 parts by weight of a rubbery polymer; And Component (2): 100 weights of one or more modified polymers selected from conjugated diene-based polymers, copolymers of conjugated diene-based monomers and vinyl aromatic hydrocarbons, or modified polymers of hydrogenation products thereof, each having one or more functional group-containing atom groups bound thereto 1 to 150 parts by weight of a master batch obtained by kneading parts and 5 to 300 parts by weight of an inorganic filler. The rubber for footwear according to claim 12, wherein component (2) is a master batch obtained by kneading after supplying 5 to 300 parts by weight of an inorganic filler into the kneader, followed by kneading, followed by addition of a modified polymer. Method of Preparation of the Composition. The method for producing a rubber composition for footwear according to claim 12, wherein component (2) is a master batch obtained by sequentially kneading 5 to 300 parts by weight of an inorganic filler in a kneader two times and then kneading them sequentially. A method for producing the master batch according to claim 1, which comprises feeding 5 to 300 parts by weight of the inorganic filler into the kneader, followed by kneading, followed by addition of the modified polymer. 20 to 80% of the inorganic filler is preliminarily fed into the kneader, followed by kneading, followed by addition of the modified polymer, then kneading, and further addition of the remaining amount of the inorganic filler followed by kneading. The manufacturing method of the masterbatch of Claim 1.